Preparation of halophosphate phosphors using antimony-doped calcium pyrophosphate

ABSTRACT

Antimony-doped calcium pyrophosphate is used as the antimonysupplying ingredient in the manufacture of calcium halophosphate phosphors activated with antimony or antimony plus manganese. The extreme fineness and high reactivity of the antimony-supplying materials and their low volatility at lower temperatures are significant advantages in the manufacture of the phosphors.

United States Patent Gillooly 5] Feb. 1, 1972 54] PREPARATION OF HALOPHOSPIIATE PHOSPHORS USING ANTIMONY- DOPED CALCIUM PYROPHOSPHATE {72] Inventor: George R. Gillooly, Cleveland Heights,

Ohio

[73] Assignee: General Electric Company [22] Filed: Jan. 28, 1970 [21] Appl. No.: 6,584

3,468,812 9/1969 Wanmaker et al. ..-...'...2s2/3o1.4 P

FOREIGN PATENTS OR APPLICATIONS 578,272 6/1946 Great Britain ..252/30l .4 P

Primary Examiner-Robert D. Edmonds Attorney-Richard H. Burgess, Henry F. Truesdell, Frank L. Neuhauser, Oscar B. Waddell and Joseph B. Forman [5 7] ABSTRACT Antimony-doped calcium pyrophosphate is used as the antimony-supplying ingredient in the manufacture of calcium halophosphate phosphors activated with antimony or antimony plus manganese. The extreme fineness and high reactivity of the antimony-supplying materials and their low volatility at lower temperatures are significant advantages in the manufacture of the phosphors.

9 Claims, No Drawings PREPARATION OF HALOPHOSPHATE PHOSPHORS USING ANTIMONY-DOPED CALCIUM PYROPHOSPHATE BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION It is an object of the present invention to provide a process for the production of calcium halophosphate phosphors in which the losses of antimony and chlorine will be much less than occurred with prior art processes. Another object is to increase the reactivity and decrease the particle size of the antimony constituent of the phosphor intermediate ingredients.

Briefly stated, the present invention provides a process of preparing an antimony-activated calcium halophosphate phosphor, said process comprising: mixing together in powdered form antimony-doped calcium pyrophosphate containing antimony in an activating amount, with ingredients reactable to form said phosphor and firing said mixture. Manganese can also be used as an optional additional activator or coactivator to obtain different colors.

The antimony-doped calcium pyrophosphate intermediate of the invention is preferably prepared by reacting CaHPO and Sb O and the resulting Ca P -,xCa(SbO is used along with, for example, CaCO and CaF to produce antimony-doped phosphors having a bluish color. Cool-white and warm-white phosphors can be produced as known in the art by also using CaCl and MnCO as additional ingredients. Preferred firing conditions, as known in the art, are temperatures in the range of l,050 to 1,200" C. for times sufficient to form efiicient phosphors such as 2 to 3 hours for large samples. Shorter times could be used for smaller samples.

The invention also includes the Ca P O-,-xCa(SbO and its method of preparation described below.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Moles MW Grams CaHPO, 6000 I385 831.0 Sb,O 0.055 291 16.0

The dicalcium phosphate preferably includes an excess of calcium in oxide form to facilitateformation of the antimonydoped calcium pyrophosphate, Ca P 0 'xCa(Sb0 in accordance with the following formula:

2CaHPO,(0.02CaO)+0.04Sb O Q2 Ca P O -0.04Ca(Sb0 1 12 l, The value of x indicated the antimony content can preferably range from 0.005 to 0.050 depending on the phosphor formulation and characteristics desired for the resulting phosphor for conventional phosphor production. Of course, other values of x could be appropriate, for example, when different ingredients or proportions are used to prepare the phosphor.

The amount of antimony may be varied to obtain the desired final antimony content as determined by variations of the furnace geometry and firing schedule in a manner familiar to the art. A typical example would be to fire about 3 kilograms about 3 hours in open silica dishes with sufficient oxygen present to oxidize the antimony and form a calcium antimonate at about 950 C., preferably the meta-antimonate.

.After such a firing the intermediate is not sintered but remains fluid and can be used after minimal crushing and screening.

EXAMPLES OF FORMULAS FOR USING Sb-DOPED PYROPHOSPHATE The following ingredients may be blended together by techniques familiar to the art:

I. BLUE HALOPHOSPHOR Intermediates Moles MW Grams Ca,P,O -xCa(SbO,), 3.00 258' 774 CaCO, 2.83 283 CaF, 0.95 78 74 When warmer color is desired, manganese and chloride are added, according to the art, and calcium and fluoride are reduced, as for example:

ll. COOL-WHITE HALOPHOSPHOR Intermediates Moles MW Grams Ca,P,O,'xCa( Sb0,), 3.00 258 774 CaCO, 2.63 I00 263 CaF, 0.89 78 69 CaCl, 0. l 0 l l I I I MnCO, 018 22.5

Or, for even warmer color, even greater substitution of manganese is used:

"I. WARM-WHITE HALOPHOSPHOR Intermediates Moles MW Ca,P,OrxCa(SbO,), 3.00 258 774 CaCO, 2.47 I00 73 CaF, 0.89 78 69 CaCl, 0.10 l l I t l MnCO, 0.34 I25 42.5

EXAMPLE OF FIRING PROCEDURE About 2 to 3 kilograms may be heated to l,l00 to l,200 C., preferably about l,l50 C. for Example II, for 2 to 3 hours in silica trays, preferably covered. The thus-fired material may be suitable for use in lamps. However, better results can be obtained if this material is crushed, blended, and fired a second time, preferably in a covered dish and in an inert atmosphere, such as nitrogen. For Example I, the preferred temperature may be somewhat higher than 1,1 50 C. for the first firing, and for Example Ill, the preferred temperature may be somewhat less than l,l50 C. for the first firing. The temperature of the second firing may be even lower if an inert atmosphere is used, preferably about 1,050 C. for all three examples.

For example, calcium meta-antimonate prepared according to the prior art and reduced in size by extremely rigorous ballmilling may attain particle sizes in the range of l-3 microns (fl), whereas the calcium meta-antimonate from the antimony-doped calcium pyrophosphate is prepared in extremely fine particles which lie almost entirely in a range below I a. The calcium pyrophosphate particles themselves preferably have sizes from Sp. to 25p.. The extreme fineness of the calcium meta-antimonate is well illustrated by the increase of surface area from 6 square meters per gram (m./g.) for the prior .art to about 30 m.'/g. for the present invention. Such an increase in surface area due to the increased fineness of the particles presents a proportionate increase in the opportunity for chemical reaction. A second advantage derived from the use of smaller particles is the greater number of particles required to obtain a given weight of the ingredient, which greater number can be distributed more uniformly throughout the batch. Moreover, when the fine particles are prepared in conjunction with the calcium pyrophosphate which is the major ingredient of the phosphor batch, more uniform dispersion is assured.

Calcium meta-antimonate particles used according to the prior art are relatively very coarse in grain and not very reactive. They distribute poorly in the batch. By comparison, materials of the invention are extremely fine powders.

What I claim as new and desire to secure by Letters Patent of the United States is:

l. The process of preparing an antimony-activated calcium halophosphate phosphor, saidprocess comprising: mixing together in powdered form antimony-doped calcium pyrophosphate containing antimony in an activating amount, with ingredients reactable to formsaid phosphor and firing said mixture.

2. The process of claim 1 in which said antimony-doped calcium pyrophosphate has been prepared by reacting together at elevated temperature CaHPO, and Sb,0, in selected quantities.

3. The process of claim 1 in which the phosphor is also activated with manganese.

4. The process of claim 1 in which the ingredients used to prepare the phosphor are Ca,P,O,:Sb, CaCO and Cal- 5. The process of claim 4 in which said ingredients are reacted together at a temperature in therange of 1,050" to l,200 C. for sufficient time to produce an efficient phosphor.

6. The process according to-claim 3 in which the ingredients are Ca,P,O :Sb, CaCO,, Ca'F,, CaCl,, and MnCO,.

7. The process according to claim 6 in which said ingredients are reacted together at a temperature in the rangeof 1,050 to l,200 C. for sufficient time to produce an efiicient phosphor.

8. An intermediate material for use in the process of claim 1 consisting essentially of antimony-doped calcium 

2. The process of claim 1 in which said antimony-doped calcium pyrophosphate has been prepared by reacting together at elevated temperature CaHPO4 and Sb2O3 in selected quantities.
 3. The process of claim 1 in which the phosphor is also activated with manganese.
 4. The process of claim 1 in which the ingredients used to prepare the phosphor are Ca2P2O7:Sb, CaCO3, and CaF2.
 5. The process of claim 4 in which said ingredients are reacted together at a temperature in the range of 1,050* to 1,200* C. for sufficient time to produce an efficient phosphor.
 6. The process according to claim 3 in which the ingredients are Ca2P2O7:Sb, CaCO3, CaF2, CaCl2, and MnCO3.
 7. The process according to claim 6 in which said ingredients are reacted together at a temperature in the range of 1,050* to 1,200* C. for sufficient time to produce an efficient phosphor.
 8. An intermediate material for use in the process of claim 1 consisting essentially of antimony-doped calcium pyrophosphate in the form of small particles of Ca2P2O7 having an average size in the range of 5 Mu to 25 Mu and in which the antimony, at least in part, is in the form of submicroN particles of calcium meta-antimonate located on the surfaces of the particles of calcium pyrophosphate.
 9. The method of preparing the intermediate material of claim 8 wherein CaHPO4 is reacted with Sb2O3, and wherein said CaHPO4 contains an excess of CaO in an amount at least great enough to react with said Sb2O3 to form Ca(SbO3)2. 